WO2009099233A1 - Diamond uv sensor element and manufacturing method thereof, uv sensor device, diamond single crystal processing method - Google Patents
Diamond uv sensor element and manufacturing method thereof, uv sensor device, diamond single crystal processing method Download PDFInfo
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- WO2009099233A1 WO2009099233A1 PCT/JP2009/052172 JP2009052172W WO2009099233A1 WO 2009099233 A1 WO2009099233 A1 WO 2009099233A1 JP 2009052172 W JP2009052172 W JP 2009052172W WO 2009099233 A1 WO2009099233 A1 WO 2009099233A1
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 111
- 239000010432 diamond Substances 0.000 title claims abstract description 111
- 239000013078 crystal Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000003672 processing method Methods 0.000 title claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 19
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000001947 vapour-phase growth Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
- G01J1/429—Photometry, e.g. photographic exposure meter using electric radiation detectors applied to measurement of ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/06—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion material in the gaseous state
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the PN heterojunction type
Abstract
Disclosed is a method for manufacturing a diamond UV sensor element with improved UV light/visible light blind ratio that uses diamond single crystal as the light-receiving part and that detects light by changes in electrical resistance generated by exposing the light-receiving part to light. Said diamond UV sensor element manufacturing method includes (1) a step for hydrogenating the surface of the diamond single crystal in an atmosphere containing essentially hydrogen and (2) a step for forming the light receiving part by exposing the surface of said hydrogenated diamond single crystal to an atmosphere containing ozone or active oxygen.
Description
本発明は、ダイヤモンド紫外線センサー素子とその製造方法、紫外線センサー装置、ダイヤモンド単結晶の処理方法に関する。
The present invention relates to a diamond ultraviolet sensor element and a manufacturing method thereof, an ultraviolet sensor device, and a diamond single crystal processing method.
ダイヤモンドは大きなバンドキャップを持つため、ダイヤモンド単結晶膜を紫外線センサー素子の受光部として用いることが知られている。例えば、従来より、メタンと水素ガスを用いたマイクロ波励起プラズマ気相成長法により、その表面が実質的に水素原子で覆われた（以下、「水素化」ともいう）ダイヤモンド単結晶膜を製造し、これを受光部とすることが知られている（例えば、特許文献１、２参照）。また、別の例としては、気相合成により一軸性に配向成長したダイヤモンド膜の表面に酸素を化学吸着した（以下、「酸素化」ともいう）紫外線検出層を有するダイヤモンド膜紫外線センサーも提案されている（例えば、特許文献３参照）。
ところで、紫外線センサー素子における受光部材料としての重要な指標として、紫外線照射下において流れる光電流値と可視光照射下で流れる光電流値の比（以下、「紫外／可視光ブラインド比」ともいう）が挙げられる。この値が大きいほど高感度の紫外線センサー素子を実現することができるため、より大きな値を持つことが望まれているのが実情である。
特開２００５－３１０９６３号公報
特開平１１－０９７７２１号公報
特開平１１－２４８５３１号公報
Since diamond has a large band cap, it is known to use a diamond single crystal film as a light receiving portion of an ultraviolet sensor element. For example, conventionally, a diamond single crystal film whose surface is substantially covered with hydrogen atoms (hereinafter also referred to as “hydrogenation”) is produced by microwave-excited plasma vapor deposition using methane and hydrogen gas. It is known that this is used as a light receiving section (see, for example, Patent Documents 1 and 2). As another example, a diamond film ultraviolet sensor having an ultraviolet detection layer in which oxygen is chemisorbed (hereinafter also referred to as “oxygenation”) on the surface of a uniaxially oriented diamond film by vapor phase synthesis has been proposed. (For example, refer to Patent Document 3).
By the way, as an important index as a light receiving part material in an ultraviolet sensor element, a ratio of a photocurrent value flowing under ultraviolet irradiation to a photocurrent value flowing under visible light irradiation (hereinafter also referred to as “ultraviolet / visible light blind ratio”). Is mentioned. The larger the value, the higher the sensitivity of the UV sensor element can be realized. Therefore, it is actually desired to have a larger value.
JP 2005-310963 A JP-A-11-097721 Japanese Patent Laid-Open No. 11-248531
ところで、紫外線センサー素子における受光部材料としての重要な指標として、紫外線照射下において流れる光電流値と可視光照射下で流れる光電流値の比（以下、「紫外／可視光ブラインド比」ともいう）が挙げられる。この値が大きいほど高感度の紫外線センサー素子を実現することができるため、より大きな値を持つことが望まれているのが実情である。
By the way, as an important index as a light receiving part material in an ultraviolet sensor element, a ratio of a photocurrent value flowing under ultraviolet irradiation to a photocurrent value flowing under visible light irradiation (hereinafter also referred to as “ultraviolet / visible light blind ratio”). Is mentioned. The larger the value, the higher the sensitivity of the UV sensor element can be realized. Therefore, it is actually desired to have a larger value.
しかしながら、表面が水素化したダイヤモンド膜は大きな暗電流が流れるため、紫外／可視光ブラインド比は比較的小さくなる。一方、ダイヤモンド表面に酸素を吸着することにより、ダイヤモンド膜表面における表面電流が抑制されて暗電流が非常に小さくなるが、紫外線照射時における光電流値も小さくなり、その結果紫外／可視光ブラインド比が小さくなる。
本発明は、以上の通りの事情に鑑みてなされたものであり、紫外／可視光ブラインド比を向上させたダイヤモンド紫外線センサー素子とその製造方法、紫外線センサー装置、ダイヤモンド単結晶の処理方法を提供することを課題としている。 However, since a large dark current flows through the diamond film whose surface is hydrogenated, the ultraviolet / visible blind ratio becomes relatively small. On the other hand, by adsorbing oxygen to the diamond surface, the surface current on the diamond film surface is suppressed and the dark current becomes very small. However, the photocurrent value at the time of ultraviolet irradiation is also reduced, resulting in the ultraviolet / visible blind ratio. Becomes smaller.
The present invention has been made in view of the circumstances as described above, and provides a diamond ultraviolet sensor element having an improved ultraviolet / visible light blind ratio, a manufacturing method thereof, an ultraviolet sensor device, and a diamond single crystal processing method. It is an issue.
本発明は、以上の通りの事情に鑑みてなされたものであり、紫外／可視光ブラインド比を向上させたダイヤモンド紫外線センサー素子とその製造方法、紫外線センサー装置、ダイヤモンド単結晶の処理方法を提供することを課題としている。 However, since a large dark current flows through the diamond film whose surface is hydrogenated, the ultraviolet / visible blind ratio becomes relatively small. On the other hand, by adsorbing oxygen to the diamond surface, the surface current on the diamond film surface is suppressed and the dark current becomes very small. However, the photocurrent value at the time of ultraviolet irradiation is also reduced, resulting in the ultraviolet / visible blind ratio. Becomes smaller.
The present invention has been made in view of the circumstances as described above, and provides a diamond ultraviolet sensor element having an improved ultraviolet / visible light blind ratio, a manufacturing method thereof, an ultraviolet sensor device, and a diamond single crystal processing method. It is an issue.
本発明は、上記の課題を解決するために、以下のことを特徴としている。
第１に、本発明は、ダイヤモンド単結晶を受光部とし、この受光部に照射される光によって生じる電気抵抗の変化で光を検出するダイヤモンド紫外線センサー素子の製造方法であって、（１）ダイヤモンド単結晶の表面を実質的に水素を含む雰囲気中で水素化する工程と、（２）前記水素化したダイヤモンド単結晶の表面をオゾンまたは活性酸素を含む雰囲気中に曝露することにより受光部を形成する工程と、を含むものである。 The present invention is characterized by the following in order to solve the above problems.
The first aspect of the present invention is a method for manufacturing a diamond ultraviolet sensor element that uses a diamond single crystal as a light receiving portion and detects light by a change in electrical resistance caused by light irradiated to the light receiving portion. A step of hydrogenating the surface of the single crystal in an atmosphere substantially containing hydrogen, and (2) forming a light receiving portion by exposing the surface of the hydrogenated diamond single crystal to an atmosphere containing ozone or active oxygen. And a step of performing.
第１に、本発明は、ダイヤモンド単結晶を受光部とし、この受光部に照射される光によって生じる電気抵抗の変化で光を検出するダイヤモンド紫外線センサー素子の製造方法であって、（１）ダイヤモンド単結晶の表面を実質的に水素を含む雰囲気中で水素化する工程と、（２）前記水素化したダイヤモンド単結晶の表面をオゾンまたは活性酸素を含む雰囲気中に曝露することにより受光部を形成する工程と、を含むものである。 The present invention is characterized by the following in order to solve the above problems.
The first aspect of the present invention is a method for manufacturing a diamond ultraviolet sensor element that uses a diamond single crystal as a light receiving portion and detects light by a change in electrical resistance caused by light irradiated to the light receiving portion. A step of hydrogenating the surface of the single crystal in an atmosphere substantially containing hydrogen, and (2) forming a light receiving portion by exposing the surface of the hydrogenated diamond single crystal to an atmosphere containing ozone or active oxygen. And a step of performing.
第２に、前記工程（２）は、表面が水素化されたダイヤモンド単結晶を収納したチャンバに酸素ガスを導入し、これに紫外線を照射することによって形成したオゾンを含む雰囲気中で行うものである。
Second, the step (2) is performed in an atmosphere containing ozone formed by introducing oxygen gas into a chamber containing a hydrogenated diamond single crystal and irradiating it with ultraviolet rays. is there.
第３に、前記ダイヤモンド単結晶が、基板上に積層されたダイヤモンド単結晶膜である。
Third, the diamond single crystal is a diamond single crystal film laminated on a substrate.
第４に、本発明は、ダイヤモンド単結晶を受光部として基板上に形成され、この受光部に照射される光によって生じる電気抵抗の変化で光を検出するダイヤモンド紫外線センサー素子であって、受光部は、表面が水素化されたダイヤモンド単結晶をオゾンまたは活性酸素を含む雰囲気中に曝露して形成されたものである。
Fourthly, the present invention is a diamond ultraviolet sensor element that is formed on a substrate using a diamond single crystal as a light receiving part and detects light by a change in electrical resistance caused by light irradiated to the light receiving part. Is formed by exposing a diamond single crystal whose surface is hydrogenated to an atmosphere containing ozone or active oxygen.
第５に、本発明の紫外線センサー装置は、上記のダイヤモンド紫外線センサー素子が、その一部として構成されているものである。
Fifth, in the ultraviolet sensor device of the present invention, the diamond ultraviolet sensor element is configured as a part thereof.
第６に、本発明は、ダイヤモンド単結晶の処理方法であって、（１）ダイヤモンド単結晶の表面を実質的に水素を含む雰囲気中で水素化する工程と、（２）前記水素化したダイヤモンド単結晶の表面をオゾンまたは活性酸素を含む雰囲気中に曝露する工程と、を含むものである。
Sixth, the present invention is a method for treating a diamond single crystal, comprising: (1) a step of hydrogenating the surface of the diamond single crystal in an atmosphere substantially containing hydrogen; and (2) the hydrogenated diamond. Exposing the surface of the single crystal to an atmosphere containing ozone or active oxygen.
第７に、上記第６の発明における工程（２）は、酸素ガスに紫外線を照射してオゾンまたは活性酸素を発生させ、このオゾンまたは活性酸素を含む雰囲気下、水素化したダイヤモンド単結晶の表面を曝露するものである。
Seventh, in the step (2) in the sixth invention, the surface of the hydrogenated diamond single crystal is generated by irradiating an oxygen gas with ultraviolet rays to generate ozone or active oxygen, and in an atmosphere containing the ozone or active oxygen. Is to be exposed.
第８に、上記第７の発明において、紫外線強度または紫外線照射時間を制御して、ダイヤモンド単結晶表面の結合水素濃度を制御するものである。
Eighth, in the seventh invention, the bond hydrogen concentration on the surface of the diamond single crystal is controlled by controlling the UV intensity or UV irradiation time.
１ 電極
２ 受光部 1 Electrode 2 Receiver
２ 受光部 1 Electrode 2 Receiver
本発明において、ダイヤモンド紫外線センサー素子とは、基板上に紫外線を検出するための受光部が形成され、さらにその受光部に接するように、例えば図１に示すような一対のくし形の電極２が形成されて構成されているものである。図１においては互いに対になるくし形の電極１の間が受光部２である。この受光部は、例えば、基板上に積層されたダイヤモンド単結晶膜の表面あるいはダイヤモンド単結晶基板の表面を、後述する処理、具体的には水素化処理およびオゾン処理を行って形成される。
In the present invention, the diamond ultraviolet sensor element includes a light receiving portion for detecting ultraviolet light on a substrate, and a pair of comb-shaped electrodes 2 as shown in FIG. It is formed and configured. In FIG. 1, a light receiving portion 2 is between the comb-shaped electrodes 1 that are paired with each other. This light receiving portion is formed, for example, by subjecting the surface of the diamond single crystal film laminated on the substrate or the surface of the diamond single crystal substrate to the treatment described later, specifically, hydrogenation treatment and ozone treatment.
本発明のダイヤモンド紫外線センサー素子の製造方法は、（１）ダイヤモンド単結晶の表面を実質的に水素を含む雰囲気中で水素化する工程と、（２）前記水素化したダイヤモンド単結晶の表面をオゾンまたは活性酸素を含む雰囲気中に曝露することにより受光部を形成する工程と、を含むことを特徴としている。
The method for producing a diamond ultraviolet sensor element according to the present invention comprises (1) a step of hydrogenating the surface of a diamond single crystal in an atmosphere substantially containing hydrogen, and (2) a surface of the hydrogenated diamond single crystal being ozone. Or a step of forming a light receiving portion by exposure to an atmosphere containing active oxygen.
上記の水素化処理工程（１）におけるダイヤモンド単結晶は、例えば、基板上に形成されたダイヤモンド単結晶膜あるいはダイヤモンド単結晶基板であってもよい。ダイヤモンド単結晶膜は、マイクロ波励起プラズマ気相成長法（例えば特公昭５９－２７７５４参照）や高周波プラズマＣＶＤ法、直流プラズマＣＶＤ法等の公知の気相合成法によりダイヤモンド単結晶基板上に合成することができる。ここでダイヤモンド単結晶膜の表面の水素化は、例えば、前記マイクロ波励起プラズマ気相成長法によるダイヤモンド単結晶膜の合成に伴って実現することができる。すなわち、この気相成長法は水素ガスを含む雰囲気中での気相成長法であるため、この方法で成長させたダイヤモンドエピタキシャル層の表面には炭素原子（Ｃ）の未結合手が水素原子（Ｈ）によって結合終端されたＣ－Ｈ分子構造が存在することになる。一方、このような水素化したエピタキシャル層を持たないダイヤモンド単結晶基板の表面の水素化については、水素を含む雰囲気中で前記気相成長法と同じ装置を用いて処理することにより実現することができる。
The diamond single crystal in the hydrogenation process (1) may be, for example, a diamond single crystal film or a diamond single crystal substrate formed on the substrate. The diamond single crystal film is synthesized on a diamond single crystal substrate by a known vapor phase synthesis method such as a microwave-excited plasma vapor phase growth method (see, for example, Japanese Patent Publication No. 59-27754), a high frequency plasma CVD method, a direct current plasma CVD method or the like. be able to. Here, hydrogenation of the surface of the diamond single crystal film can be realized, for example, with the synthesis of the diamond single crystal film by the microwave-excited plasma vapor deposition method. That is, since this vapor phase growth method is a vapor phase growth method in an atmosphere containing hydrogen gas, dangling bonds of carbon atoms (C) are present on the surface of the diamond epitaxial layer grown by this method. There will be a CH molecular structure terminated by H). On the other hand, hydrogenation of the surface of a diamond single crystal substrate having no hydrogenated epitaxial layer can be realized by processing using the same apparatus as the vapor phase growth method in an atmosphere containing hydrogen. it can.
水素化したダイヤモンド単結晶表面についてさらに説明すると、水素化処理したダイヤモンド単結晶表面には、水素化に伴って表面近傍のダイヤモンド内にキャリアの正孔が局在した２次元的な表面伝導層が発生していることが知られている。この表面伝導層の発生機構は、現在学会において世界的にも大論争段階にあり不明である。しかしながら、この表面伝導層は少なくとも実験的には（１）雰囲気温度２００℃程度までは安定に存在し、（２）水素化されたダイヤモンド表面にのみ発生しており、（３）表面伝導層の面抵抗は５～１０ｋΩ／□である、ことがわかっている。この表面伝導層は、表面の結合水素を除去する処理（酸化処理）、例えば、沸騰させた硫酸・硝酸混合液中に浸す処理を施すことによって消滅することも知られている。すなわち、ダイヤモンド表面の電気伝導層の有無を測定することによって、ダイヤモンド表面が水素化されているかどうかを判別することができる。
The hydrogenated diamond single crystal surface will be further described. The hydrogenated diamond single crystal surface has a two-dimensional surface conductive layer in which carrier holes are localized in diamond in the vicinity of the surface with hydrogenation. It is known that it has occurred. The generation mechanism of this surface conductive layer is currently unknown at the academic conference worldwide. However, this surface conductive layer is at least experimentally stable (1) up to an atmospheric temperature of about 200 ° C., (2) occurs only on the hydrogenated diamond surface, and (3) the surface conductive layer It is known that the sheet resistance is 5 to 10 kΩ / □. It is also known that this surface conductive layer disappears by performing a treatment (oxidation treatment) for removing bonded hydrogen on the surface, for example, a treatment immersed in a boiled sulfuric acid / nitric acid mixture. That is, by measuring the presence or absence of an electrically conductive layer on the diamond surface, it can be determined whether or not the diamond surface is hydrogenated.
上記のオゾンまたは活性酸素処理工程（２）は、前記水素化したダイヤモンド単結晶の表面を、オゾンまたは活性酸素、あるいはそれら両者を含む雰囲気中に、例えば、室温で５分から５０時間程度、低圧水銀ランプの紫外線とともに曝露して酸化処理している。なお、このような処理を以下、単に、オゾン処理とも呼ぶ。オゾンまたは活性酸素は、上記水素化したダイヤモンド単結晶が配置されたオゾン処理装置内に酸素（Ｏ２）ガスを導入し、この酸素（Ｏ２）ガスに紫外線を照射したり、あるいは無声放電することで発生させることができる。より具体的には、酸素（Ｏ２）ガスに低圧水銀ランプの紫外線を照射することにより、以下の反応過程を通して、オゾン（Ｏ３）および活性酸素（Ｏ）が生成されるものと考えられる。
生成されたオゾンおよび活性酸素とダイモンド表面の結合水素が反応して、揮発性分子（ＣＯ２，Ｈ２Ｏ等）となりダイヤモンド表面から脱離する。そして未結合手は、酸素（Ｏ）あるいは酸素水素分子（ＯＨ）等によって結合されると考えられる。 In the ozone or active oxygen treatment step (2), the surface of the hydrogenated diamond single crystal is placed in an atmosphere containing ozone or active oxygen or both, for example, at room temperature for about 5 minutes to 50 hours, under low pressure mercury. It is exposed to the ultraviolet rays of the lamp and oxidized. Hereinafter, such treatment is also simply referred to as ozone treatment. Ozone or active oxygen, the hydrogenated diamond single crystal oxygen disposed ozone processing device (O 2) introducing a gas, or irradiated with ultraviolet rays to the oxygen gas (O 2), or silent discharge Can be generated. More specifically, it is considered that ozone (O 3 ) and active oxygen (O) are generated through the following reaction process by irradiating oxygen (O 2 ) gas with ultraviolet rays from a low-pressure mercury lamp.
The generated ozone and active oxygen react with hydrogen bonded to the diamond surface to form volatile molecules (CO 2 , H 2 O, etc.) and desorb from the diamond surface. The dangling bonds are considered to be bound by oxygen (O) or oxygen-hydrogen molecules (OH).
生成されたオゾンおよび活性酸素とダイモンド表面の結合水素が反応して、揮発性分子（ＣＯ２，Ｈ２Ｏ等）となりダイヤモンド表面から脱離する。そして未結合手は、酸素（Ｏ）あるいは酸素水素分子（ＯＨ）等によって結合されると考えられる。 In the ozone or active oxygen treatment step (2), the surface of the hydrogenated diamond single crystal is placed in an atmosphere containing ozone or active oxygen or both, for example, at room temperature for about 5 minutes to 50 hours, under low pressure mercury. It is exposed to the ultraviolet rays of the lamp and oxidized. Hereinafter, such treatment is also simply referred to as ozone treatment. Ozone or active oxygen, the hydrogenated diamond single crystal oxygen disposed ozone processing device (O 2) introducing a gas, or irradiated with ultraviolet rays to the oxygen gas (O 2), or silent discharge Can be generated. More specifically, it is considered that ozone (O 3 ) and active oxygen (O) are generated through the following reaction process by irradiating oxygen (O 2 ) gas with ultraviolet rays from a low-pressure mercury lamp.
The generated ozone and active oxygen react with hydrogen bonded to the diamond surface to form volatile molecules (CO 2 , H 2 O, etc.) and desorb from the diamond surface. The dangling bonds are considered to be bound by oxygen (O) or oxygen-hydrogen molecules (OH).
本発明におけるオゾン処理の利点は、紫外線強度や酸素（Ｏ２）ガスへの紫外線の照射時間を制御することによって、上記反応式（１）、（２）の反応速度を制御でき、これによりダイヤモンド表面の結合水素（ＣＨ）濃度を制御することができる点にある。したがって、ダイヤモンド表面における上記表面伝導層の面抵抗を制御でき、紫外光センサーの紫外光／可視光ブラインド比を容易に制御することができる。即ち、ダイヤモンド表面伝導層内の正孔濃度は表面におけるＣＨ濃度に比例するため、ダイヤモンド表面の結合状態がＣＯあるいはＣＯＨに変換することによって正孔濃度は減少する。なお、水素化したダイヤモンド単結晶表面を酸素化処理するにあたり、上記オゾン処理以外に、例えば１９０～２３０℃に沸騰させた混酸溶液で処理する方法が考えられる。しかしながら、この処理方法ではダイヤモンド単結晶表面の結合水素を完全に除去することが難しく、また、原子的描像によってダイヤモンド単結晶表面の未結合手を酸素原子によって終端させることが難しい等の欠点がある。本発明におけるオゾン処理は、ダイヤモンド単結晶表面のクリーニング化と同時に酸素原子あるいは酸素水素分子終端を可能にするプロセッシングであり、上記のような欠点を克服するものでもある。
The advantage of the ozone treatment in the present invention is that the reaction rate of the above reaction formulas (1) and (2) can be controlled by controlling the ultraviolet intensity and the irradiation time of ultraviolet rays to the oxygen (O 2 ) gas. It exists in the point which can control the surface hydrogen bond (CH) density | concentration of a surface. Therefore, the surface resistance of the surface conductive layer on the diamond surface can be controlled, and the ultraviolet light / visible light blind ratio of the ultraviolet light sensor can be easily controlled. That is, since the hole concentration in the diamond surface conductive layer is proportional to the CH concentration on the surface, the hole concentration is reduced by converting the bonding state of the diamond surface to CO or COH. In addition, when oxygenating the hydrogenated diamond single crystal surface, in addition to the ozone treatment, a method of treating with a mixed acid solution boiled at 190 to 230 ° C., for example, can be considered. However, this treatment method has the disadvantages that it is difficult to completely remove the bonded hydrogen on the surface of the diamond single crystal, and it is difficult to terminate the dangling bonds on the surface of the diamond single crystal with oxygen atoms by atomic imaging. . The ozone treatment in the present invention is a processing that enables oxygen atom or oxygen hydrogen molecule termination at the same time as the cleaning of the surface of the diamond single crystal, and overcomes the above drawbacks.
本発明は、以上のようにその表面が水素化したダイヤモンド単結晶をオゾン処理することで、これによって得たダイヤモンド紫外線センサー素子の紫外／可視光ブラインド比を、従来の水素化したダイヤモンド単結晶膜を受光部としたダイヤモンド紫外線センサー素子に比べて、１～３桁程度増加させることが可能である。さらに、オゾン処理時間を制御して、ダイヤモンド紫外線センサー素子の受光感度と応答速度の制御も可能となる。
このようにして得られたダイヤモンド紫外線センサー素子は、例えば、工業用燃焼炉、ガスタービンエンジン、ジェットエンジン等の燃焼制御モニターや火災探知機と連動した炎探知機用の火炎センサーあるいは紫外線照射装置内の紫外線センサーとして用いることができる。
以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって本発明が限定されることはない。 The present invention provides a conventional hydrogenated diamond single crystal film in which the ultraviolet / visible light blind ratio of a diamond ultraviolet sensor element obtained by performing ozone treatment on the diamond single crystal whose surface is hydrogenated as described above is a conventional one. It can be increased by about 1 to 3 orders of magnitude compared with a diamond ultraviolet sensor element using a light receiving portion. Furthermore, it is possible to control the light reception sensitivity and response speed of the diamond ultraviolet sensor element by controlling the ozone treatment time.
The diamond ultraviolet sensor element thus obtained can be used in, for example, a combustion sensor for an industrial combustion furnace, a gas turbine engine, a jet engine or the like, a flame sensor for a flame detector linked to a fire detector, or an ultraviolet irradiation device. It can be used as an ultraviolet sensor.
Hereinafter, examples will be shown and described in more detail. Of course, the present invention is not limited to the following examples.
このようにして得られたダイヤモンド紫外線センサー素子は、例えば、工業用燃焼炉、ガスタービンエンジン、ジェットエンジン等の燃焼制御モニターや火災探知機と連動した炎探知機用の火炎センサーあるいは紫外線照射装置内の紫外線センサーとして用いることができる。
以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって本発明が限定されることはない。 The present invention provides a conventional hydrogenated diamond single crystal film in which the ultraviolet / visible light blind ratio of a diamond ultraviolet sensor element obtained by performing ozone treatment on the diamond single crystal whose surface is hydrogenated as described above is a conventional one. It can be increased by about 1 to 3 orders of magnitude compared with a diamond ultraviolet sensor element using a light receiving portion. Furthermore, it is possible to control the light reception sensitivity and response speed of the diamond ultraviolet sensor element by controlling the ozone treatment time.
The diamond ultraviolet sensor element thus obtained can be used in, for example, a combustion sensor for an industrial combustion furnace, a gas turbine engine, a jet engine or the like, a flame sensor for a flame detector linked to a fire detector, or an ultraviolet irradiation device. It can be used as an ultraviolet sensor.
Hereinafter, examples will be shown and described in more detail. Of course, the present invention is not limited to the following examples.
＜表面が水素化したダイヤモンド単結晶膜の作製＞
ダイヤモンドエピタキシャル単結晶膜はマイクロ波プラズマ気相成長（ＭＰＣＶＤ）法により、Ｉｂ型（１００）面方位ダイヤモンド単結晶基板上に成長された。成長条件は以下のとおりである。
下地基板：Ｉｂ型（１００）面方位ダイヤモンド単結晶基板（エレメントシックス社製）
原料ガス：メタン（ＣＨ４）、流量０．４ｓｃｃｍ
キャリアー（希釈）ガス：水素（Ｈ２）、流量５００ｓｃｃｍ
ＣＨ４／Ｈ２濃度比：０．０８％（ｖｏｌ）
成長中圧力：８０Ｔｏｒｒ
マイクロ波パワー：４００Ｗ
基板温度：９３０℃
成長時間：４時間
エピタキシャル単結晶膜の厚さ：０．２５μｍ
成長終了後、即ち、メタンガスの供給を止めた後、エピタキシャル単結晶膜を１０分間水素雰囲気下で基板温度に保った。 <Preparation of hydrogen single-crystal diamond film>
The diamond epitaxial single crystal film was grown on an Ib type (100) -oriented diamond single crystal substrate by a microwave plasma vapor deposition (MPCVD) method. The growth conditions are as follows.
Base substrate: Ib type (100) plane oriented diamond single crystal substrate (manufactured by Element Six)
Source gas: Methane (CH 4 ), flow rate 0.4 sccm
Carrier (dilution) gas: hydrogen (H 2 ),flow rate 500 sccm
CH 4 / H 2 concentration ratio: 0.08% (vol)
Growth pressure: 80 Torr
Microwave power: 400W
Substrate temperature: 930 ° C
Growth time: 4 hours Epitaxial single crystal film thickness: 0.25 μm
After the growth was completed, that is, after the supply of methane gas was stopped, the epitaxial single crystal film was kept at the substrate temperature in a hydrogen atmosphere for 10 minutes.
ダイヤモンドエピタキシャル単結晶膜はマイクロ波プラズマ気相成長（ＭＰＣＶＤ）法により、Ｉｂ型（１００）面方位ダイヤモンド単結晶基板上に成長された。成長条件は以下のとおりである。
下地基板：Ｉｂ型（１００）面方位ダイヤモンド単結晶基板（エレメントシックス社製）
原料ガス：メタン（ＣＨ４）、流量０．４ｓｃｃｍ
キャリアー（希釈）ガス：水素（Ｈ２）、流量５００ｓｃｃｍ
ＣＨ４／Ｈ２濃度比：０．０８％（ｖｏｌ）
成長中圧力：８０Ｔｏｒｒ
マイクロ波パワー：４００Ｗ
基板温度：９３０℃
成長時間：４時間
エピタキシャル単結晶膜の厚さ：０．２５μｍ
成長終了後、即ち、メタンガスの供給を止めた後、エピタキシャル単結晶膜を１０分間水素雰囲気下で基板温度に保った。 <Preparation of hydrogen single-crystal diamond film>
The diamond epitaxial single crystal film was grown on an Ib type (100) -oriented diamond single crystal substrate by a microwave plasma vapor deposition (MPCVD) method. The growth conditions are as follows.
Base substrate: Ib type (100) plane oriented diamond single crystal substrate (manufactured by Element Six)
Source gas: Methane (CH 4 ), flow rate 0.4 sccm
Carrier (dilution) gas: hydrogen (H 2 ),
CH 4 / H 2 concentration ratio: 0.08% (vol)
Growth pressure: 80 Torr
Microwave power: 400W
Substrate temperature: 930 ° C
Growth time: 4 hours Epitaxial single crystal film thickness: 0.25 μm
After the growth was completed, that is, after the supply of methane gas was stopped, the epitaxial single crystal film was kept at the substrate temperature in a hydrogen atmosphere for 10 minutes.
以上の方法により、表面が水素化されたダイヤモンドエピタキシャル単結晶膜を得る。エピタキシャル単結晶膜を持たないダイヤモンド単結晶基板については、上記の成長装置と同じ装置を用いて、以下の条件により水素化処理をすることで、表面が水素化されたダイヤモンド単結晶基板を得ることができる。
マイクロ波パワー：４００Ｗ
水素（Ｈ２）流量：５００ｓｃｃｍ
基板温度：９００℃
処理時間：１時間 By the above method, a diamond epitaxial single crystal film having a hydrogenated surface is obtained. For a diamond single crystal substrate that does not have an epitaxial single crystal film, a hydrogen single-crystal diamond substrate is obtained by performing hydrogenation treatment under the following conditions using the same apparatus as the above growth apparatus. Can do.
Microwave power: 400W
Hydrogen (H 2 ) flow rate: 500 sccm
Substrate temperature: 900 ° C
Processing time: 1 hour
マイクロ波パワー：４００Ｗ
水素（Ｈ２）流量：５００ｓｃｃｍ
基板温度：９００℃
処理時間：１時間 By the above method, a diamond epitaxial single crystal film having a hydrogenated surface is obtained. For a diamond single crystal substrate that does not have an epitaxial single crystal film, a hydrogen single-crystal diamond substrate is obtained by performing hydrogenation treatment under the following conditions using the same apparatus as the above growth apparatus. Can do.
Microwave power: 400W
Hydrogen (H 2 ) flow rate: 500 sccm
Substrate temperature: 900 ° C
Processing time: 1 hour
＜デバイス（ダイヤモンド紫外線センサー素子）の作製＞
上記で作製したダイヤモンドエピタキシャル単結晶膜上に、ＷＣおよびＷＣ／Ａｕ（ここで“／”は積層順序を示す）を電極材料とするくし形電極構造作製のためのレジストのパターニングを行った。その後、スパッタリング法によりＷＣおよびＡｕターゲット材のスパッタリングから第１層にＷＣ、続いて第２層にＡｕを積層堆積させ、リフトオフ法により電極を作製した。図１は作製したくし形電極構造のデバイスの表面写真である。この図において、黒色の部分が受光部２としてのダイヤモンドエピタキシャル単結晶膜である。一つのデバイスの大きさは２７０μｍ×８００μｍであり、くし形電極１の間隔は１０μｍであった。 <Production of device (diamond UV sensor element)>
On the diamond epitaxial single crystal film produced as described above, resist patterning for producing a comb-shaped electrode structure using WC and WC / Au (here, “/” indicates the stacking order) as an electrode material was performed. Thereafter, WC and Au target material were sputtered by sputtering to deposit and deposit WC on the first layer and then Au to the second layer, and an electrode was fabricated by lift-off method. FIG. 1 is a photograph of the surface of a device having a fabricated comb electrode structure. In this figure, the black portion is a diamond epitaxial single crystal film as thelight receiving portion 2. The size of one device was 270 μm × 800 μm, and the interval between the comb electrodes 1 was 10 μm.
上記で作製したダイヤモンドエピタキシャル単結晶膜上に、ＷＣおよびＷＣ／Ａｕ（ここで“／”は積層順序を示す）を電極材料とするくし形電極構造作製のためのレジストのパターニングを行った。その後、スパッタリング法によりＷＣおよびＡｕターゲット材のスパッタリングから第１層にＷＣ、続いて第２層にＡｕを積層堆積させ、リフトオフ法により電極を作製した。図１は作製したくし形電極構造のデバイスの表面写真である。この図において、黒色の部分が受光部２としてのダイヤモンドエピタキシャル単結晶膜である。一つのデバイスの大きさは２７０μｍ×８００μｍであり、くし形電極１の間隔は１０μｍであった。 <Production of device (diamond UV sensor element)>
On the diamond epitaxial single crystal film produced as described above, resist patterning for producing a comb-shaped electrode structure using WC and WC / Au (here, “/” indicates the stacking order) as an electrode material was performed. Thereafter, WC and Au target material were sputtered by sputtering to deposit and deposit WC on the first layer and then Au to the second layer, and an electrode was fabricated by lift-off method. FIG. 1 is a photograph of the surface of a device having a fabricated comb electrode structure. In this figure, the black portion is a diamond epitaxial single crystal film as the
＜オゾン処理＞
上記デバイスについてオゾン処理を行った。オゾン処理は、市販されているＵＶオゾンクリーナー（ＵＶ／２５３型、日本レーザー電子）装置を用いて室温において行った。このプロセスにおいて、まずオゾンクリーナーチャンバ（２００×２０７×１４２ｍｍ）内の空気を除去するために、酸素ガス（Ｏ２）を導入した。低圧水銀ランプを用いて紫外線強度３．７ｍＷ／ｃｍ２を照射することによって、チャンバ内の酸素から、前記反応式（１）および（２）によりオゾン（Ｏ３）および活性酸素（Ｏ）が形成された。
ここで、チャンバ内への酸素ガス導入は、酸素ガスをチャンバ内に一定時間連続フローさせ、チャンバ内を酸素で充填させることによって行っている。そして前記反応式（１）および（２）によりオゾン（Ｏ３）および活性酸素（Ｏ）を形成させるために、チャンバ内で紫外線を照射し、同一チャンバ内に水素化ダイヤモンド表面にセンサーを作製した上記デバイスを配置することによって、低圧水銀ランプ紫外線を照射すると同時にオゾン処理を行っている。
このプロセスにおいて付加的な酸素ガスをチャンバ内に導入することは無かった。オゾン処理時間は、数分から数十時間の範囲で変化させた。ここで、オゾン処理時間とは、チャンバ内に導入した酸素ガスに紫外線を照射している時間である。 <Ozone treatment>
The device was subjected to ozone treatment. The ozone treatment was performed at room temperature using a commercially available UV ozone cleaner (UV / 253 type, Nippon Laser Electronics) apparatus. In this process, oxygen gas (O 2 ) was first introduced to remove air in the ozone cleaner chamber (200 × 207 × 142 mm). Irradiation with an ultraviolet intensity of 3.7 mW / cm 2 using a low-pressure mercury lamp forms ozone (O 3 ) and active oxygen (O) from the oxygen in the chamber according to the reaction formulas (1) and (2). It was done.
Here, the oxygen gas is introduced into the chamber by continuously flowing oxygen gas into the chamber for a certain period of time and filling the chamber with oxygen. Then, in order to form ozone (O 3 ) and active oxygen (O) by the reaction formulas (1) and (2), ultraviolet rays were irradiated in the chamber, and a sensor was produced on the surface of the hydrogenated diamond in the same chamber. By arranging the above devices, ozone treatment is performed at the same time as irradiation with ultraviolet light from a low-pressure mercury lamp.
No additional oxygen gas was introduced into the chamber during this process. The ozone treatment time was changed in the range of several minutes to several tens of hours. Here, the ozone treatment time is the time during which the oxygen gas introduced into the chamber is irradiated with ultraviolet rays.
上記デバイスについてオゾン処理を行った。オゾン処理は、市販されているＵＶオゾンクリーナー（ＵＶ／２５３型、日本レーザー電子）装置を用いて室温において行った。このプロセスにおいて、まずオゾンクリーナーチャンバ（２００×２０７×１４２ｍｍ）内の空気を除去するために、酸素ガス（Ｏ２）を導入した。低圧水銀ランプを用いて紫外線強度３．７ｍＷ／ｃｍ２を照射することによって、チャンバ内の酸素から、前記反応式（１）および（２）によりオゾン（Ｏ３）および活性酸素（Ｏ）が形成された。
ここで、チャンバ内への酸素ガス導入は、酸素ガスをチャンバ内に一定時間連続フローさせ、チャンバ内を酸素で充填させることによって行っている。そして前記反応式（１）および（２）によりオゾン（Ｏ３）および活性酸素（Ｏ）を形成させるために、チャンバ内で紫外線を照射し、同一チャンバ内に水素化ダイヤモンド表面にセンサーを作製した上記デバイスを配置することによって、低圧水銀ランプ紫外線を照射すると同時にオゾン処理を行っている。
このプロセスにおいて付加的な酸素ガスをチャンバ内に導入することは無かった。オゾン処理時間は、数分から数十時間の範囲で変化させた。ここで、オゾン処理時間とは、チャンバ内に導入した酸素ガスに紫外線を照射している時間である。 <Ozone treatment>
The device was subjected to ozone treatment. The ozone treatment was performed at room temperature using a commercially available UV ozone cleaner (UV / 253 type, Nippon Laser Electronics) apparatus. In this process, oxygen gas (O 2 ) was first introduced to remove air in the ozone cleaner chamber (200 × 207 × 142 mm). Irradiation with an ultraviolet intensity of 3.7 mW / cm 2 using a low-pressure mercury lamp forms ozone (O 3 ) and active oxygen (O) from the oxygen in the chamber according to the reaction formulas (1) and (2). It was done.
Here, the oxygen gas is introduced into the chamber by continuously flowing oxygen gas into the chamber for a certain period of time and filling the chamber with oxygen. Then, in order to form ozone (O 3 ) and active oxygen (O) by the reaction formulas (1) and (2), ultraviolet rays were irradiated in the chamber, and a sensor was produced on the surface of the hydrogenated diamond in the same chamber. By arranging the above devices, ozone treatment is performed at the same time as irradiation with ultraviolet light from a low-pressure mercury lamp.
No additional oxygen gas was introduced into the chamber during this process. The ozone treatment time was changed in the range of several minutes to several tens of hours. Here, the ozone treatment time is the time during which the oxygen gas introduced into the chamber is irradiated with ultraviolet rays.
＜電気的・光学的特性結果＞
上記オゾン処理後のデバイスについて、暗電流（光照射無しの状態における電流値）および紫外線照射時の光電流と印加電圧との関係を調べた。図２は、波長２２０ｎｍの紫外線照射時および暗条件における電流－印加電圧特性を示す。図２中、黒丸はオゾン処理前であって、表面が水素化された状態のデバイスのデータを示しており、１）、２）、３）の矢印で示すデータはそれぞれ、オゾン処理を８０分、４時間、２４時間行ったデバイスのデータを示している。ここで、暗条件における電流のデータにおいて、２）および３）の矢印で示すデータは同じであり検出限界以下である。
この図からオゾン処理が紫外線照射時の光電流値の減少をもたらすばかりでなく、さらに暗電流の減少をもたらす。すなわち、紫外光オン／オフ時の電流値の差を増加させる。水素化表面は導電性を持つために、成長させた後の水素化表面においては、紫外光オン／オフ時の電流値は非常に悪くなることが確認された。 <Results of electrical and optical characteristics>
About the device after the said ozone treatment, the relationship between the dark current (current value in the state without light irradiation) and the photocurrent at the time of ultraviolet irradiation and the applied voltage was examined. FIG. 2 shows current-applied voltage characteristics when irradiated with ultraviolet light having a wavelength of 220 nm and under dark conditions. In FIG. 2, the black circles represent the data of the device before the ozone treatment and the surface was hydrogenated, and the data indicated by the arrows 1), 2) and 3) represent the ozone treatment for 80 minutes. Data of devices performed for 4 hours and 24 hours are shown. Here, in the current data in the dark condition, the data indicated by the arrows 2) and 3) are the same and below the detection limit.
From this figure, the ozone treatment not only reduces the photocurrent value during ultraviolet irradiation, but also reduces the dark current. That is, the difference in current value when the ultraviolet light is on / off is increased. Since the hydrogenated surface has conductivity, it was confirmed that the current value at the time of turning on / off the ultraviolet light on the hydrogenated surface after the growth was extremely deteriorated.
上記オゾン処理後のデバイスについて、暗電流（光照射無しの状態における電流値）および紫外線照射時の光電流と印加電圧との関係を調べた。図２は、波長２２０ｎｍの紫外線照射時および暗条件における電流－印加電圧特性を示す。図２中、黒丸はオゾン処理前であって、表面が水素化された状態のデバイスのデータを示しており、１）、２）、３）の矢印で示すデータはそれぞれ、オゾン処理を８０分、４時間、２４時間行ったデバイスのデータを示している。ここで、暗条件における電流のデータにおいて、２）および３）の矢印で示すデータは同じであり検出限界以下である。
この図からオゾン処理が紫外線照射時の光電流値の減少をもたらすばかりでなく、さらに暗電流の減少をもたらす。すなわち、紫外光オン／オフ時の電流値の差を増加させる。水素化表面は導電性を持つために、成長させた後の水素化表面においては、紫外光オン／オフ時の電流値は非常に悪くなることが確認された。 <Results of electrical and optical characteristics>
About the device after the said ozone treatment, the relationship between the dark current (current value in the state without light irradiation) and the photocurrent at the time of ultraviolet irradiation and the applied voltage was examined. FIG. 2 shows current-applied voltage characteristics when irradiated with ultraviolet light having a wavelength of 220 nm and under dark conditions. In FIG. 2, the black circles represent the data of the device before the ozone treatment and the surface was hydrogenated, and the data indicated by the arrows 1), 2) and 3) represent the ozone treatment for 80 minutes. Data of devices performed for 4 hours and 24 hours are shown. Here, in the current data in the dark condition, the data indicated by the arrows 2) and 3) are the same and below the detection limit.
From this figure, the ozone treatment not only reduces the photocurrent value during ultraviolet irradiation, but also reduces the dark current. That is, the difference in current value when the ultraviolet light is on / off is increased. Since the hydrogenated surface has conductivity, it was confirmed that the current value at the time of turning on / off the ultraviolet light on the hydrogenated surface after the growth was extremely deteriorated.
次に、オゾン処理後の４個のデバイスついて、オゾン処理時間に対する暗電流および受光感度の変化を調べた。図３はオゾン処理時間に対する暗電流の変化を示し、図４はオゾン処理時間に対する受光感度の変化を示す。受光感度は２２０ｎｍ光を照射した時の光電流値から換算した。オゾン処理時間は８０分、４時間、２４時間とした。また、オゾン処理前であって表面が水素化された状態のデバイス、および表面を酸素化処理した状態のデバイスについても暗電流と受光感度を測定した。
これら図３および図４の結果から、表面が水素化された状態のデバイスでは、大きな暗電流（～６×１０－４Ａ、図３）および受光感度（＞５×１０５Ａ／Ｗ、図４）となっている。８０分のオゾン処理後においては、暗電流は１０桁程度劇的に減少する。一方、受光感度はデバイスに依存するが１～３桁程度減少する。さらに続けてオゾン処理すると、暗電流はオゾン処理よってほとんど変化しないが、受光感度はさらに４～２０Ａ／Ｗまで減少する（図４）。この受光感度値は、図４の“＋”印に示した酸素化処理表面の受光感度値１×１０－３Ａ／Ｗに比べてかなり大きい値に保たれていることがわかる。 Next, changes in dark current and light receiving sensitivity with respect to the ozone treatment time were examined for the four devices after the ozone treatment. FIG. 3 shows changes in dark current with respect to ozone treatment time, and FIG. 4 shows changes in light receiving sensitivity with respect to ozone treatment time. The light receiving sensitivity was converted from the photocurrent value when 220 nm light was irradiated. The ozone treatment time was 80 minutes, 4 hours, and 24 hours. In addition, the dark current and the light receiving sensitivity were measured for a device in which the surface was hydrogenated before the ozone treatment and a device in which the surface was oxygenated.
From the results shown in FIGS. 3 and 4, in the device having a hydrogenated surface, a large dark current ( ˜6 × 10 −4 A, FIG. 3) and light receiving sensitivity (> 5 × 10 5 A / W, FIG. 4). After 80 minutes of ozone treatment, the dark current decreases dramatically by about 10 orders of magnitude. On the other hand, the light receiving sensitivity is reduced by about 1 to 3 digits depending on the device. When the ozone treatment is further continued, the dark current is hardly changed by the ozone treatment, but the light receiving sensitivity is further reduced to 4 to 20 A / W (FIG. 4). It can be seen that this light receiving sensitivity value is maintained at a considerably higher value than the light receivingsensitivity value 1 × 10 −3 A / W of the oxygenated surface shown by the “+” mark in FIG.
これら図３および図４の結果から、表面が水素化された状態のデバイスでは、大きな暗電流（～６×１０－４Ａ、図３）および受光感度（＞５×１０５Ａ／Ｗ、図４）となっている。８０分のオゾン処理後においては、暗電流は１０桁程度劇的に減少する。一方、受光感度はデバイスに依存するが１～３桁程度減少する。さらに続けてオゾン処理すると、暗電流はオゾン処理よってほとんど変化しないが、受光感度はさらに４～２０Ａ／Ｗまで減少する（図４）。この受光感度値は、図４の“＋”印に示した酸素化処理表面の受光感度値１×１０－３Ａ／Ｗに比べてかなり大きい値に保たれていることがわかる。 Next, changes in dark current and light receiving sensitivity with respect to the ozone treatment time were examined for the four devices after the ozone treatment. FIG. 3 shows changes in dark current with respect to ozone treatment time, and FIG. 4 shows changes in light receiving sensitivity with respect to ozone treatment time. The light receiving sensitivity was converted from the photocurrent value when 220 nm light was irradiated. The ozone treatment time was 80 minutes, 4 hours, and 24 hours. In addition, the dark current and the light receiving sensitivity were measured for a device in which the surface was hydrogenated before the ozone treatment and a device in which the surface was oxygenated.
From the results shown in FIGS. 3 and 4, in the device having a hydrogenated surface, a large dark current ( ˜6 × 10 −4 A, FIG. 3) and light receiving sensitivity (> 5 × 10 5 A / W, FIG. 4). After 80 minutes of ozone treatment, the dark current decreases dramatically by about 10 orders of magnitude. On the other hand, the light receiving sensitivity is reduced by about 1 to 3 digits depending on the device. When the ozone treatment is further continued, the dark current is hardly changed by the ozone treatment, but the light receiving sensitivity is further reduced to 4 to 20 A / W (FIG. 4). It can be seen that this light receiving sensitivity value is maintained at a considerably higher value than the light receiving
次に、受光感度および応答時間のオゾン処理時間依存性について調べた（図５）。オゾン処理時間は８０分、４時間、２４時間とした。図５の左縦軸が受光感度を示し、右縦軸が２２０ｎｍ光オフ後の光電流過渡応答における減衰時間を示す。この図５から、８０分のオゾン処理後には、長い応答時間が観察された。これは光照射オフ後に観察される「永続的光伝導」として知られているものである。さらにオゾン処理時間を長くすると応答時間が減少する。受光感度はオゾン処理時間が長いほど減少することが確認された。
Next, the dependence of the light receiving sensitivity and response time on the ozone treatment time was examined (FIG. 5). The ozone treatment time was 80 minutes, 4 hours, and 24 hours. The left vertical axis in FIG. 5 indicates the light receiving sensitivity, and the right vertical axis indicates the decay time in the photocurrent transient response after the 220 nm light is turned off. From FIG. 5, a long response time was observed after 80 minutes of ozone treatment. This is known as “permanent photoconduction” observed after light irradiation is turned off. Furthermore, if the ozone treatment time is lengthened, the response time decreases. It was confirmed that the light receiving sensitivity decreased as the ozone treatment time increased.
さらに、紫外／可視光ブラインド比のオゾン処理時間依存性について調べた（図６）。オゾン処理時間は８０分、４時間、２４時間とした。ここで、紫外／可視光ブラインド比は、波長２１０ｎｍおよび４００ｎｍの同一光強度の紫外線および可視光線照射したときの光電流値の比と定義する。この図６から、オゾン処理後のデバイスの紫外／可視光ブラインド比は、表面が水素化した状態のデバイスと比べると、１～３桁程度増加していることが確認された。
なお、図３－図６の横軸はそれぞれオゾン処理時間を示しており、いずれの図においても横軸の目盛り５．０（ｈ）と２２．５（ｈ）の間のオゾン処理時間を一部省略して記載しているが、その省略した区間での縦軸の値はほとんど変化していない。 Furthermore, the ozone treatment time dependency of the ultraviolet / visible light blind ratio was examined (FIG. 6). The ozone treatment time was 80 minutes, 4 hours, and 24 hours. Here, the ultraviolet / visible light blind ratio is defined as a ratio of photocurrent values when irradiated with ultraviolet rays and visible rays having the same light intensity at wavelengths of 210 nm and 400 nm. From FIG. 6, it was confirmed that the ultraviolet / visible light blind ratio of the device after the ozone treatment increased by about 1 to 3 digits as compared with the device having a hydrogenated surface.
The horizontal axis in FIGS. 3 to 6 indicates the ozone treatment time, and in each figure, the ozone treatment time between the scales 5.0 (h) and 22.5 (h) on the horizontal axis is set to one. Although the part is omitted, the value on the vertical axis in the omitted section hardly changes.
なお、図３－図６の横軸はそれぞれオゾン処理時間を示しており、いずれの図においても横軸の目盛り５．０（ｈ）と２２．５（ｈ）の間のオゾン処理時間を一部省略して記載しているが、その省略した区間での縦軸の値はほとんど変化していない。 Furthermore, the ozone treatment time dependency of the ultraviolet / visible light blind ratio was examined (FIG. 6). The ozone treatment time was 80 minutes, 4 hours, and 24 hours. Here, the ultraviolet / visible light blind ratio is defined as a ratio of photocurrent values when irradiated with ultraviolet rays and visible rays having the same light intensity at wavelengths of 210 nm and 400 nm. From FIG. 6, it was confirmed that the ultraviolet / visible light blind ratio of the device after the ozone treatment increased by about 1 to 3 digits as compared with the device having a hydrogenated surface.
The horizontal axis in FIGS. 3 to 6 indicates the ozone treatment time, and in each figure, the ozone treatment time between the scales 5.0 (h) and 22.5 (h) on the horizontal axis is set to one. Although the part is omitted, the value on the vertical axis in the omitted section hardly changes.
本発明は、従来のダイヤモンド紫外線センサー素子よりも、さらに紫外／可視光ブラインド比を向上させたダイヤモンド紫外線センサー素子を、非常に簡便な方法によって得ることができる。さらに本発明は、オゾンまたは活性酸素を含む雰囲気中での処理時間を変えることで、ダイヤモンド紫外線センサー素子の受光感度および応答速度を容易に制御することができる。
得られるダイヤモンド紫外線センサー素子は、表面が水素化された従来のダイヤモンド単結晶膜を受光部としたものに比べ、紫外／可視光ブラインド比を１～３桁程度増加させることも可能であり、工業用燃焼炉、ガスタービンエンジン、ジェットエンジン等の燃焼制御モニターや火災探知機と連動した炎探知機用の火炎センサーあるいは紫外線照射装置内の紫外線センサー等として有用である。
According to the present invention, a diamond ultraviolet sensor element in which the ultraviolet / visible blind ratio is further improved as compared with the conventional diamond ultraviolet sensor element can be obtained by a very simple method. Furthermore, according to the present invention, the light receiving sensitivity and response speed of the diamond ultraviolet sensor element can be easily controlled by changing the processing time in an atmosphere containing ozone or active oxygen.
The resulting diamond ultraviolet sensor element can increase the UV / visible blind ratio by about 1 to 3 digits compared to the conventional diamond single crystal film with hydrogenated surface as the light receiving part. It is useful as a combustion control monitor for a combustion furnace, a gas turbine engine, a jet engine, etc., a flame sensor for a flame detector linked to a fire detector, or an ultraviolet sensor in an ultraviolet irradiation device.
得られるダイヤモンド紫外線センサー素子は、表面が水素化された従来のダイヤモンド単結晶膜を受光部としたものに比べ、紫外／可視光ブラインド比を１～３桁程度増加させることも可能であり、工業用燃焼炉、ガスタービンエンジン、ジェットエンジン等の燃焼制御モニターや火災探知機と連動した炎探知機用の火炎センサーあるいは紫外線照射装置内の紫外線センサー等として有用である。
According to the present invention, a diamond ultraviolet sensor element in which the ultraviolet / visible blind ratio is further improved as compared with the conventional diamond ultraviolet sensor element can be obtained by a very simple method. Furthermore, according to the present invention, the light receiving sensitivity and response speed of the diamond ultraviolet sensor element can be easily controlled by changing the processing time in an atmosphere containing ozone or active oxygen.
The resulting diamond ultraviolet sensor element can increase the UV / visible blind ratio by about 1 to 3 digits compared to the conventional diamond single crystal film with hydrogenated surface as the light receiving part. It is useful as a combustion control monitor for a combustion furnace, a gas turbine engine, a jet engine, etc., a flame sensor for a flame detector linked to a fire detector, or an ultraviolet sensor in an ultraviolet irradiation device.
Claims (8)
- ダイヤモンド単結晶を受光部とし、この受光部に照射される光によって生じる電気抵抗の変化で光を検出するダイヤモンド紫外線センサー素子の製造方法であって、
（１）ダイヤモンド単結晶の表面を実質的に水素を含む雰囲気中で水素化する工程と、
（２）前記水素化したダイヤモンド単結晶の表面をオゾンまたは活性酸素を含む雰囲気中に曝露することにより受光部を形成する工程と、
を含むことを特徴とするダイヤモンド紫外線センサー素子の製造方法。 A method for manufacturing a diamond ultraviolet sensor element that uses a diamond single crystal as a light receiving portion and detects light by a change in electrical resistance caused by light irradiated to the light receiving portion,
(1) hydrogenating the surface of the diamond single crystal in an atmosphere substantially containing hydrogen;
(2) forming a light receiving portion by exposing the surface of the hydrogenated diamond single crystal to an atmosphere containing ozone or active oxygen;
A method for producing a diamond ultraviolet ray sensor element, comprising: - 前記工程（２）は、表面が水素化されたダイヤモンド単結晶を収納したチャンバに酸素ガスを導入し、これに紫外線を照射することによって形成したオゾンまたは活性酸素を含む雰囲気中で行うものであることを特徴とする請求項１に記載のダイヤモンド紫外線センサー素子の製造方法。 The step (2) is performed in an atmosphere containing ozone or active oxygen formed by introducing oxygen gas into a chamber containing a hydrogenated diamond single crystal and irradiating it with ultraviolet rays. The method for producing a diamond ultraviolet ray sensor element according to claim 1.
- 前記ダイヤモンド単結晶が、基板上に積層されたダイヤモンド単結晶膜であることを特徴とする請求項１または２に記載のダイヤモンド紫外線センサー素子の製造方法。 3. The method for producing a diamond ultraviolet sensor element according to claim 1, wherein the diamond single crystal is a diamond single crystal film laminated on a substrate.
- ダイヤモンド単結晶を受光部として基板上に形成され、この受光部に照射される光によって生じる電気抵抗の変化で光を検出するダイヤモンド紫外線センサー素子であって、受光部は、表面が水素化されたダイヤモンド単結晶をオゾンまたは活性酸素を含む雰囲気中に曝露して形成されたものであることを特徴とするダイヤモンド紫外線センサー素子。 A diamond ultraviolet sensor element that is formed on a substrate with a diamond single crystal as a light receiving portion and detects light by a change in electrical resistance caused by light irradiated to the light receiving portion. The light receiving portion has a hydrogenated surface. A diamond ultraviolet ray sensor element formed by exposing a diamond single crystal to an atmosphere containing ozone or active oxygen.
- 請求項４のダイヤモンド紫外線センサー素子が、その一部として構成されていることを特徴とする紫外線センサー装置。 An ultraviolet sensor device comprising the diamond ultraviolet sensor element according to claim 4 as a part thereof.
- ダイヤモンド単結晶の処理方法であって、
（１）ダイヤモンド単結晶の表面を実質的に水素を含む雰囲気中で水素化する工程と、
（２）前記水素化したダイヤモンド単結晶の表面をオゾンまたは活性酸素を含む雰囲気中に曝露する工程と、
を含むことを特徴とするダイヤモンド単結晶の処理方法。 A method for processing a diamond single crystal,
(1) hydrogenating the surface of the diamond single crystal in an atmosphere substantially containing hydrogen;
(2) exposing the surface of the hydrogenated diamond single crystal to an atmosphere containing ozone or active oxygen;
The processing method of the diamond single crystal characterized by including these. - 請求項６における工程（２）は、酸素ガスに紫外線を照射してオゾンまたは活性酸素を発生させ、このオゾンまたは活性酸素を含む雰囲気下、水素化したダイヤモンド単結晶の表面を曝露することを特徴とするダイヤモンド単結晶の処理方法。 The step (2) in claim 6 is characterized in that the oxygen gas is irradiated with ultraviolet rays to generate ozone or active oxygen, and the surface of the hydrogenated diamond single crystal is exposed in an atmosphere containing the ozone or active oxygen. A method for processing a diamond single crystal.
- 紫外線強度または紫外線照射時間を制御して、ダイヤモンド単結晶表面の結合水素濃度を制御する請求項７に記載のダイヤモンド単結晶の処理方法。
The method for treating a diamond single crystal according to claim 7, wherein the bond hydrogen concentration on the surface of the diamond single crystal is controlled by controlling the ultraviolet intensity or the ultraviolet irradiation time.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09708514.6A EP2246896B1 (en) | 2008-02-07 | 2009-02-09 | Diamond uv sensor element and manufacturing method thereof, uv sensor device, diamond single crystal processing method |
| US12/866,554 US8435597B2 (en) | 2008-02-07 | 2009-02-09 | Diamond UV-sensor element and manufacturing method thereof, UV-sensor unit, and method of treating diamond single crystal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008027232A JP5504565B2 (en) | 2008-02-07 | 2008-02-07 | Diamond UV sensor element, manufacturing method thereof, and UV sensor device |
| JP2008-027232 | 2008-02-07 |
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| WO2009099233A1 true WO2009099233A1 (en) | 2009-08-13 |
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| PCT/JP2009/052172 WO2009099233A1 (en) | 2008-02-07 | 2009-02-09 | Diamond uv sensor element and manufacturing method thereof, uv sensor device, diamond single crystal processing method |
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| Country | Link |
|---|---|
| US (1) | US8435597B2 (en) |
| EP (1) | EP2246896B1 (en) |
| JP (1) | JP5504565B2 (en) |
| WO (1) | WO2009099233A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120178201A1 (en) * | 2010-02-05 | 2012-07-12 | Hitachi Chemical Company, Ltd. | Composition for forming n-type diffusion layer, method for forming n-type diffusion layer, and method for producing photovoltaic cell |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2650090C1 (en) * | 2016-10-27 | 2018-04-06 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Photoconverter of ultraviolet range |
| DE102018209549A1 (en) | 2018-06-14 | 2019-12-19 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | UV radiation sensor based on diamond |
| US11397301B2 (en) * | 2018-06-21 | 2022-07-26 | Howard University | Sensors including a housing, a diamond diaphragm, and an optical cable, and methods of manufacturing the sensors |
| RU2745906C1 (en) * | 2020-02-18 | 2021-04-02 | Общество с ограниченной ответственностью "Даймонд ин сайнс" | Image receiver and converter |
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- 2009-02-09 WO PCT/JP2009/052172 patent/WO2009099233A1/en active Application Filing
- 2009-02-09 EP EP09708514.6A patent/EP2246896B1/en not_active Not-in-force
- 2009-02-09 US US12/866,554 patent/US8435597B2/en not_active Expired - Fee Related
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| JPS5927754B2 (en) | 1981-12-17 | 1984-07-07 | 科学技術庁無機材質研究所長 | Diamond synthesis method |
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| US20120178201A1 (en) * | 2010-02-05 | 2012-07-12 | Hitachi Chemical Company, Ltd. | Composition for forming n-type diffusion layer, method for forming n-type diffusion layer, and method for producing photovoltaic cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5504565B2 (en) | 2014-05-28 |
| EP2246896A4 (en) | 2014-12-31 |
| EP2246896A1 (en) | 2010-11-03 |
| JP2009188222A (en) | 2009-08-20 |
| US20110045173A1 (en) | 2011-02-24 |
| EP2246896B1 (en) | 2017-08-09 |
| US8435597B2 (en) | 2013-05-07 |
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